KR101897632B1 - Diarylfluorene amine derivative organic compounds and organic electroluminescent device including the same - Google Patents

Abstract

상기 식에서, R¹, R², R³, R⁴, R⁵, R, n, Ar_, X 및 L은 전술하여 정의된 바와 같다.There is provided a diarylfluoreneamine derivative organic compound represented by the following formula (a).
<Formula a>

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R, n, Ar _, X and L are as defined above.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a diarylfluorene amine derivative organic compound and an organic electroluminescent device including the same. BACKGROUND ART &lt; RTI ID = 0.0 &gt;

Diarylfluoreneamine derivative compounds and organic electroluminescent devices comprising the same.

An electroluminescence device (EL device) is a self-emissive type display device having a high response speed and a wide viewing angle. In 1987, Eastman Kodak Company first developed an organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer material [Appl. Phys. Lett. 51, 913, 1987].

The most important factor for determining the luminous efficiency in an organic electroluminescent device is a luminescent material. The phosphorescent material of the luminescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent material. Until now, iridium (III) complexes and carbazole-based materials have been widely known as phosphorescent materials, and new phosphorescent materials are being studied in recent years.

The principle of organic electroluminescent phenomenon is that when a voltage is applied between two electrodes when an organic thin film layer exists between a cathode and an anode, electrons and holes are injected into the organic thin film layer from the cathode and the anode, respectively. Electrons and holes injected into the organic thin film layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic electroluminescent device using this principle can be generally constituted of an organic thin film layer including a cathode, an anode and an organic thin film layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Most of materials used in organic electroluminescent devices are pure organic materials or complexes in which an organic material and a metal form a complex with each other. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, Can be distinguished. As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material which is easily oxidized and electrochemically stable at the time of oxidation, is mainly used. On the other hand, as an electron injecting material and an electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and electrochemically stable at the time of reduction is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable. Accordingly, there is a need in the art to develop new organic materials having the above-described requirements.

One embodiment of the present invention provides novel diarylfluoreneamine derivative compounds having appropriate energy levels, electrochemical stability, and thermal stability.

Another embodiment of the present invention provides an organic electroluminescent device comprising the diarylfluorenamine derivative compound.

In one embodiment of the present invention, there is provided a diarylfluoreneamine derivative compound represented by the following formula (a).

<Formula a>

In this formula,

R ¹ to R ⁵ each independently represent hydrogen, deuterium, halogen, C 1 to C 12 alkoxy, amino, nitrile, C 2 to C 12 acyl, C 3 to C 12 silyl or substituted or unsubstituted C 6 to C 60 And R ¹ to R ⁵ may form a condensed ring of C 5 to C 30 while forming a 5-membered to 6-membered ring, and the substituents when R ¹ to R ⁵ are substituted may be C ¹ to C 30 A C1 to C12 alkoxy group or a C6 to C30 aryl group,

n is an integer of 0 to 4, which are the same as or different from each other,

L is a single bond, a substituted or unsubstituted C6-C60 arylene, or a combination thereof, and when L is substituted, the substituent may be a C1-C12 alkyl group, a C1-C12 alkoxy group Or a C6 to C30 aryl group,

X is an O, S or C (R) ₂ group, each R is independently C1 to C6 alkyl or C6 to C60 aryl group, and the two Rs are connected to each other to form a spiro structure Can,

Ar is a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group, and when the Ar is substituted, the substituent is a C1-C30 alkyl group, a C6-C30 aryl group Or a C5-C30 heteroaryl group.

In another embodiment of the present invention, at least one organic thin film layer is sandwiched between a cathode and an anode, wherein the organic thin film layer has a multilayer structure including at least one light emitting layer, and the light emitting layer or the light emitting layer Wherein at least one layer in the organic thin film layer comprises the diarylfluorene amine derivative compound alone or a mixture of two or more thereof.

The diarylfluorene amine derivative compound can satisfactorily satisfy conditions required for a material usable in an organic electroluminescent device, for example, an appropriate energy level, an electrochemical stability, and a thermal stability, and the organic electroluminescent device Can play a variety of roles as required by &lt; RTI ID = 0.0 &gt;

Fig. 1 shows the 1H-NMR measurement results of Compound 6. Fig.
2 shows the results of DSC measurement of Compound 6.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless defined otherwise, the term "substituted" in the present specification means a C1-C50 alkyl group, a C3-C50 cycloalkyl group, a C2-C50 alkenyl group, a C3-C50 cycloalkenyl group, a C2-C50 alkynyl group , A C5-C50 cycloalkynyl group, a cyano group, a C1-C20 alkoxy group, a C3-C50 alkylsilyl group, a C6-C60 aryl group and a C7-C60 arylalkyl group, . &Lt; / RTI &gt;

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

"Hetero" as used herein, unless otherwise defined, means containing a heteroatom in one compound or substituent, wherein the heteroatom is selected from the group consisting of N, O, S, P, Lt; / RTI &gt; For example, it may mean one to three heteroatoms in the one compound or substituent, and the remainder is carbon.

In one embodiment of the present invention, there is provided a novel diarylfluorenamine derivative compound represented by the following formula (a).

<Formula a>

R ¹ to R ⁵ each independently represent hydrogen, deuterium, halogen, C 1 to C 12 alkoxy, amino, nitrile, C 2 to C 12 acyl, C 3 to C 12 silyl or substituted or unsubstituted C 6 to C 60 And R ¹ to R ⁵ may form a condensed ring of C 5 to C 30 while forming a 5-membered to 6-membered ring, and the substituents when R ¹ to R ⁵ are substituted may be C ¹ to C 30 A C1 to C12 alkoxy group or a C6 to C30 aryl group,

n is an integer of 0 to 4, which are the same as or different from each other,

L is a single bond, a substituted or unsubstituted C6-C60 arylene, or a combination thereof, and when L is substituted, the substituent may be a C1-C12 alkyl group, a C1-C12 alkoxy group Or a C6 to C30 aryl group,

X is an O, S or C (R) ₂ group, each R is independently C1 to C6 alkyl or C6 to C60 aryl group, and the two Rs are connected to each other to form a spiro structure Can,

Ar is a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group, and when the Ar is substituted, the substituent is a C1-C30 alkyl group, a C6-C30 aryl group Or a C5-C30 heteroaryl group.

Specifically, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthalene group or a substituted or unsubstituted fluorene group, and when L is substituted, the substituent is C1-C12 An alkyl group of C1-C12, an alkoxy group of C1-C12 or an aryl group of C6-C30.

More specifically, Ar represents a phenyl group, a heptylphenyl group, a naphthyl group, a biphenyl group, a phenanthrene group, a fluorene group, a spirobifluorene group, a benzothiophene group, a benzofuran group, a dibenzofurane group, , A naphthobenzofuran group, a terphenyl group, a carbazole group or a triphenylene group.

Specifically, when L is a phenylene group, the substitution position may be 1,4-substituted or 1,2-substituted.

In one embodiment, the formula (a) may be represented by the following formulas (b) to (c).

<Formula b>

<Formula c>

In the above formula (b) or (c)

R 1, R 2, R 3, R 4, R 5, R 6, n, Ar _, X and L are as defined in Formula a above.

For example, the diarylfluoreneamine derivative compound may be any one of compounds 1 to 113 described in Table 1 below.

When the diarylfluorene amine derivative compound is used as a material for an organic electroluminescent device, it is preferable that the diarylfluorene amine derivative compound satisfies conditions required for a material usable in an organic electroluminescent device, such as appropriate energy level, electrochemical stability and thermal stability Depending on the substituent, it can play various roles required in the organic electroluminescent device.

In another embodiment of the present invention, at least one organic thin film layer is sandwiched between a cathode and an anode, wherein the organic thin film layer has a multilayer structure including at least one light emitting layer, and the light emitting layer or the light emitting layer At least one layer in the organic thin film layer contains the diarylfluorene amine derivative compound alone or a mixture of two or more thereof.

The diarylfluorene amine derivative compound contained in the organic thin film layer of the organic electroluminescent device is a compound represented by the above formula (a), and a detailed description thereof is as described above.

In one embodiment, the organic thin film layer may suitably include at least one selected from the group consisting of a hole transporting layer, a hole injecting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer and an electron blocking layer.

In another embodiment, the organic thin film layer is disposed between the anode and the light emitting layer and includes a hole transporting layer, a hole transporting layer, a hole transporting region including at least one of a functional layer having both a hole injecting function and a hole transporting function, . &Lt; / RTI &gt;

The hole transporting region may further include a p-dopant.

The hole injection layer, the hole transport layer, the functional layer, the buffer layer, the electron blocking layer, the hole blocking layer of the light emitting layer, and the electron injection layer may be formed using known materials, And one or more kinds of an organic amine derivative compound.

A detailed description of the organic thin film layer is as described above.

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

( Example )

Hereinafter, the reaction examples and the comparative examples are specifically exemplified, but the present invention is not limited to the following reaction examples and examples. In the following reaction examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the numbers of the compounds are represented by the numbers of the formulas shown in Table 1 above. For example, compounds designated 1 in Table 1 are designated Compound 1.

[Reaction Scheme 1]

Preparation of intermediate compound [6-1]

To a 2 L reaction flask under nitrogen was added 65 g (210.22 mmol) of 1-bromo-3,5-diphenyl, 64.1 g (252.26 mmol) of bis (pinacolato) diboron, 61.9 g (630.66 mmol) 7.7 g (10.51 mmol) of palladium (II) dichloride, 650 ml of 1,4-dioxane, and the temperature is raised. After refluxing for 3 hours, the reaction mixture is filtered through celite and extracted with dichloromethane and distilled water. The organic layer is treated with anhydrous magnesium sulfate and concentrated under reduced pressure. The product was purified by silica gel chromatography and then recrystallized from dichloromethane and methanol to obtain 68.3 g (91%) of a white solid intermediate compound [6-1] .

Preparation of intermediate compound [6-2]

In a nitrogen atmosphere, 41.6 g (181.77 mmol) of 1- (2-bromo-5-methoxyphenyl) ethanone, 68 g (190.86 mmol) of the compound [6-1] and 410 ml of 1,4- And raise the temperature. 4.24 g (3.64 mmol) of tetrakis (triphenylphosphine) palladium (0) and 75.4 g (545.33 mmol) of potassium carbonate dissolved in distilled water were added at 60 ° C, followed by stirring at reflux overnight. When the reaction is completed, the reaction mixture is cooled to room temperature, and extracted with ethyl acetate and distilled water. The organic layer is treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to obtain 64.7 g (94%) of intermediate compound [6-2] in a clear oil state.

Preparation of intermediate compound [6-3]

64.7 g (170.86 mmol) of the compound [6-2] and 650 ml of tetrahydrofuran were placed in a 2 L reaction flask under a nitrogen atmosphere, and 256 ml (768.88 mmol) of methylmagnesium chloride (3.0 M in THF) Lt; / RTI &gt; After completion of the reaction, slowly drop the reaction mixture into 1.5 L of distilled water. The mixture is extracted with ethylacetate and distilled water to obtain an organic layer, which is treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain 53.9 g (80%) of intermediate compound [6-3] as a white solid.

Preparation of intermediate compound [6-4]

53.9 g (136.66 mmol) of the compound [6-3] and 540 ml of dichloromethane are introduced into a 2 L reaction flask under a nitrogen atmosphere. Methanesulfonic acid (22.2 ml, 341.65 mmol) was slowly added dropwise at 0 ° C and stirred for 2 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane and an aqueous solution of sodium chloride to obtain an organic layer, which was treated with anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel chromatography and recrystallized with toluene to obtain 42.2 g (82%) of an intermediate compound [6-4] as a white solid.

Preparation of intermediate compound [6-5]

42 g (111.55 mmol) of the compound [6-4] and 400 ml of dichloromethane are introduced into a 1 L reaction flask under a nitrogen atmosphere. 18.3 ml (189.64 mmol) of boron tribromide was slowly added dropwise at 0 ° C, stirred at room temperature for 2 hours, and the reaction was terminated. The reaction mixture is slowly added dropwise to an aqueous solution of sodium bicarbonate and extracted with dichloromethane and distilled water. The organic layer was treated with anhydrous magnesium sulfate, and then concentrated under reduced pressure. Recrystallization from dichloromethane and hexane gave 38 g (94%) of an off-white solid intermediate compound [6-5] .

Preparation of intermediate compound [6-6]

38 g (104.86 mmol) of the compound [6-5] and 390 ml of dichloromethane are introduced into a 1 L reaction flask under a nitrogen atmosphere. 17.1 ml (209.71 mmol) of pyridine is slowly added dropwise at 0 ° C, and then 25.8 ml (157.29 mmol) of anhydrous trifluoromethanesulfone is slowly added dropwise. After reacting at room temperature for 2 hours, 300 ml of distilled water is slowly added and extracted. The organic layer is subjected to anhydrous magnesium sulfate treatment and silica filtration and concentration under reduced pressure. Recrystallization from dichloromethane and hexane gave 44 g (85%) of intermediate compound [6-6] as white solid.

Preparation of compound [6]

(88.98 mmol) of compound [6-6], N - ([1,1'-biphenyl] -4- yl) -9,9- (Diphenylphosphino) - (2,2,2-trifluoroethyl) diphenylphosphonium chloride, 30.6g (84.53mmol) of amine, 12.8g (133.46mmol) of sodium tallow butoxide, 2.4g 3.1 g (5.34 mmol) of 9,9-dimethylzane and 440 ml of o-xylene were charged and refluxed and stirred for 3 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, distilled water, and anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The residue was purified by silica gel chromatography, and recrystallized from toluene to obtain 33.3 g (53%) of the target compound [6] as a white solid.

[Reaction Scheme 2]

Preparation of intermediate compound [88-1]

25.5 g (50.55 mmol) of the compound [6-6], 9.5 g (60.66 mmol) of (4-chlorophenyl) boronic acid and 250 ml of 1,4-dioxane were added to a 2 L reaction flask under a nitrogen atmosphere. 1.2 g (1.01 mmol) of tetrakis (triphenylphosphine) palladium (0) was added at 60 ° C, 10.5 g (75.83 mmol) of potassium carbonate dissolved in distilled water was added, and the mixture was refluxed with stirring for 5 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, and then concentrated under reduced pressure. The silica gel chromatograph was separated and purified to obtain 16.6 g (72%) of intermediate compound [88-1] as a white solid.

Preparation of compound [88]

(36.40 mmol) of the compound [88-1], N- (9,9-dimethyl-9H-fluoren-2-yl) dibenzo [b, (Dibenzylideneacetone) dipalladium (0), 1.0 g (1.09 mmol) of 4,5-bis (diphenylphosphino) -amine, 12.9 g (34.57 mmol) 13.9 g (48%) of the target compound [88] as a white solid were prepared by using 1.3 g (2.18 mmol) of 2,2-dimethyl-9,9-dimethylzantane and 170 ml of o-xylene.

[Reaction Scheme 3]

Preparation of intermediate compound [108-1]

(58.94 mmol) of 1- (2-bromo-3-methoxyphenyl) ethanone, 20 g (56.14 mmol) of compound [6-1], tetrakis (89% ) of Intermediate Compound [108-1] in a clear oil state was obtained by using 1.4 g (1.18 mmol) of triphenylphosphine palladium (0), 16.3 g (117.88 mmol) of potassium carbonate and 200 ml of 1,4- ).

Preparation of intermediate compound [108-2]

(52.45 mmol) of the compound [108-1], 78.7 ml (236.05 mmol) of methylmagnesium chloride (3.0 M in THF), 7.8 ml (119.60 mmol) of methanesulfonic acid, 12.7 g of an intermediate compound [108-2] as a white solid was prepared using 5.6 ml (57.61 mmol) of anhydrous trifluoromethanesulfone and 7.6 ml (46.26 mmol) of anhydrous trifluoromethanesulfone.

Preparation of compound [108]

12.7 g (25.60 mmol) of the compound [108-5], N- (9,9-dimethyl-9H-fluoren-4-yl) -9,9-dimethyl- (Dibenzylideneacetone) dipalladium (0), 0.7 g (0.77 mmol) of 4,5-bis (diphenyl) (51%) of the target compound [108] as a white solid were prepared by using 0.9 g (1.54 mmol) of o-xylene and 0.9 g of 2,2'-azobisisobutyronitrile.

According to the production methods of the above Reaction Schemes 1 to 3, Compound 1 to Compound 113 and Compound 114 of the following structural formula were prepared as Comparative Examples and the results are shown in Table 2 below.

Compound No. ^{1 H NMR (400 MHz, THF} -d 8): δ MS /
Q- TOF (M +) &lt; One (T, 3H), 7.18 (t, 2H), 7.92 (d, 2H) 2H), 6.71-6.65 (m, 3H), 6.53-6.48 (m, 4H), 1.62 (s, 12H) 629 2 (T, 3H), 7.18 (t, 2H), 7.92 (d, 2H) 2H), 2.24 (s, 6H), 1.62 (s, 12H), 6.65 (s, 657 3 2H), 7.45 (d, 1H), 7.29-7.18 (m, 6H), 7.92 (s, 6H), 1.62 (s, 12H), &lt; RTI ID = 0.0 &gt; 657 4 2H), 7.48 (d, 1H), 7.28 (t, 1H), 7.18 (t, 1H) , 7.10 (t, 2H), 6.71-6.65 (m, 3H), 6.53-6.48 (m, 4H) 679 5 (D, 2H), 7.45 (d, 1H), 7.29-7.10 (m, 12H), 6.71-6.65 (m, 3H), 6.53 ~ 6.48 (m, 4H), 1.62 (s, 12H) 665 6 2H), 1.43 (s, 6H), 1.30 (s, 2H), 8.06 (d, 1H), 7.83 (d, 6H) 705 7 (M, 12H), 1.22 (s, 6H), 7.85-7.84 (m, 2H) ), 1.08 (s, 6 H) 705 8 2H), 7.48-7.41 (m, 12H), 7.31-7.28 (t, 4H), 7.18 (t, 1H), 7.06 (t, 1H), 6.98 (d, 2H), 6.77 (s, 2H), 6.65 ) 705 9 2H), 7.52 (d, 2H), 7.45-7.41 (m, 7H), 7.31-7.18 (m, 6H), 1.62 (s, 12H), 7.09 (d, 2H) 733 10 2H), 7.45-7.28 (m, 13H), 7.18 (t, 1H), 6.65 (s, 1H) 2H), 6.59 (d, 2H), 6.48 (d, 2H), 1.62 850 11 (M, 9H), 6.65 (s, 1H), 7.62 (s, 1H) 2H), 6.59 (d, 2H), 6.48 (d, 2H), 1.62 (s, 12H) 858 12 1H), 7.45 (s, 1H), 7.52-7.41 (m, 15H), 7.31-7.28 (d, 2H), 8.45 t, 2H), 7.18 (t, IH), 6.65-6.59 (m, 4H) 806 13 1H), 7.18 (t, 1H), 7.92-7.90 (m, 5H), 7.82-7.77 (d, 3H), 7.63-7.62 ), 6.65 (s, 2H), 6.59 (d, 2H), 6.48 806 14 1H), 7.62 (s, 1H), 7.52-7.41 (m, 9H), 7.31-7.28 (m, t, 2H), 7.18 (t, IH), 6.65-6.59 (m, 4H) 906 15 (M, 9H), 7.06 (t, 2H), 7.92 (s, 1H) 1H), 6.98 (d, 2H), 6.62 (s, 2H) 858 16 2H), 7.18 (t, 1H), 7.92-7.90 (m, 5H), 7.82-7.75 (m, 3H) ), 7.06 (t, IH), 6.98 (d, 2H), 6.77 (t, IH), 6.65 (s, 2H), 7.59 (d, 806 17 1H), 7.62 (s, 1H), 7.52-7.41 (m, 6H), 7.31-7.28 (m, (m, 3H), 6.65 (d, 2H), 7.18 (t, 1H) 906 18 1H), 7.45 (s, 1H), 7.52-7.41 (m, 12H), 7.31-7.28 (d, 2H) (t, 2H), 7.18 (t, IH), 7.06 (t, IH), 6.98 (d, 2H), 6.77 , &Lt; / RTI &gt; 2H), 1.62 (s, 12H) 806 19 2H), 7.45-7.28 (m, 19H), 7.18-7.15 (m, 5H), 6.65 (s, 2H), 6.59 (d, 2H), 6.48 (d, 2H), 1.62 (s, 12H) 782 20 2H), 7.45-7.28 (m, 19H), 7.18 (t, 1H), 6.65 (s, 1H) 2H), 6.59 (d, 2H), 6.48 (d, 2H), 1.62 (s, 12H) 782 21 2H), 6.59 (d, 2H), 7.92 (s, 1H), 7.92 (s, 2H), 6.48 (d, 2H), 1.62 (s, 12H) 782 22 (M, 5H), 7.06 (t, 2H), 7.92 (d, 2H) 1H), 6.77 (d, 2H), 1.62 (s, 12H) 782 23 2H), 7.45-7.28 (m, 19H), 7.18 (t, 1H), 6.65 (s, 2H) , 6.59 (d, 2H), 6.48 (d, 2H), 2.11-1.86 (m, 4H), 1.62 (s, 6H), 1.46-1.36 731 24 (M, 3H), 7.52 (d, 2H), 7.45 ~ 7.18 (m, 22H), 7.09 ~ 7.06 (d, 4H), 6.65 d, 2H), 6.59 (d, 2H), 6.48 (dd, 2H), 1.62 828 25 2H), 7.45-7.16 (m, 26H), 7.01 (d, 4H), 6.65 (d, 2H) , 6.59 (d, 2H), 6.48 (dd, 2H), 1.62 (s, 6H) 830 26 (M, 3H), 7.18 (m, 2H), 7.92 (d, IH) 2H), 1.47 (m, 4H), 1.62 (s, 6H), 7.17 (d, 2H) ), 1.21-1.19 (m, 16H), 0.78 (m, 6H) 770 27 2H), 7.48 (d, 1H), 7.28 (t, 1H), 7.18 (t, 1H) , 7.10 (t, 2H), 6.71-6.65 (m, 3H), 6.53-6.48 (m, 4H) 679 28 2H), 7.45 (dd, 1H), 7.3-7.18 (m, 10H), 7.1 (t, 2H) 2H), 6.49 (d, 2H), 6.71 (d, 2H), 6.71 (d, 1.21 ~ 1.19 (m, 12H), 0.78 (m, 6H) 798 29 (D, 2H), 7.45-7.41 (m, 7H), 7.31-7.18 (m, 11H), 6.65 (s, (M, 2H), 6.59 (d, 2H), 6.48 (dd, 2H), 2.52 (t, 4H), 1.62 , 6H) 874 30 2H), 7.41-7.41 (m, 4H), 7.31-7.18 (m, 11H), 7.06 (d, 2H), 6.65 (d, 2H), 6.65 (d, 2H), 6.65 (d, ), 1.49 (m, 4H), 1.21-1.19 (m, 12H), 0.78 (m, 6H) 874 31 (M, 4H), 7.18 (m, 2H), 7.92 (d, 2H) 2H), 6.65 (d, 3H), 6.48 (dd, 3H), 1.62 745 32 (M, 4H), 7.18 (m, 2H), 7.92 (d, 2H) 2H), 6.65 (d, 3H), 6.48 (dd, 3H), 2.11-1.86 (m, 4H) 771 33 (M, 12H), 6.65 (d, 2H), 7.65 (d, 2H) d, 3H), 6.48 (dd, 3H), 1.62 (s, 12H) 867 34 (M, 12H), 7.01 (dd, 2H), 7.92 (d, 2H) 4H), 6.65 (d, 3H), 6.48 (dd, 3H), 1.62 869 35 2H), 7.62 (d, 1H), 7.56-7.52 (m, 4H), 7.45-7.41 (m, 9H), 7.33-7.18 6.65 (d, 2H), 6.48 (dd, 2H), 6.23 (dd, 719 36 7.92 (d, 1H), 7.79-7.77 (m, 2H), 7.62 (d, 1H), 7.56-7.52 (m, 3H), 7.45-7.41 (m, 9H), 7.31-7.15 1H), 6.62 (d, 2H), 6.97 (d, 2H) 719 37 7.92 (d, 1H), 7.79 (m, 2H), 7.62 (d, 1H), 7.56-7.52 (m, 4H), 7.45-7.41 (m, 9H), 7.31-7.18 6.65 (d, 2H), 6.48 (dd, 2H), 6.29 (dd, 719 38 (M, 4H), 7.2-7.18 (m, 2H), 7.92 (d, (m, 3H), 6.94 (d, 1H), 6.65 (d, 2H), 6.48 (dd, 2H) 745 39 (M, 13H), 7.01 (dd, 2H), 7.92 (d, 2H) 2H), 6.48 (dd, 2H), 6.38 (dd, 1H), 1.62 (s, 12H) 869 40 (M, 4H), 7.18 (d, 2H), 7.92 (d, 2H) (D, 2H), 6.93 (d, 1H), 6.81 (d, 745 41 (M, 4H), 7.18 (d, 2H), 7.92 (d, 2H) 2H), 1.86 (m, 2H), 1.62 (s, 12H), 6.91 (d, ) 1.46-1.36 (m, 4H) 771 42 (M, 12H), 7.01 (dd, 2H), 7.92 (d, 2H) 2H), 6.48 (dd, 3H), 1.62 (s, 12H) 869 43 (M, 12H), 6.93 (d, 2H), 7.92 (d, 2H) (d, 1H), 6.81 (dd, 1H), 6.65 867 44 1H), 7.88 (d, 1H), 7.72 (d, 1H), 7.97-7.92 (m, 3H) dd, 1 H), 6.65 (d, 2H), 6.48 (dd, 2H), 1.62 679 45 (D, 2H), 7.92 (d, 1H), 7.78-7.72 (m, 5H), 7.62 1H), 6.81 (d, 1H), 6.65 (d, 2H), 6.48 (dd, 2H), 1.62 729 46 2H), 7.45-7.26 (m, 15H), 7.18 (m, 1H), 6.65 (m, 2H) d, 2H), 6.48 (dd, 2H), 1.62 (s, 12H) 679 47 1H), 7.85 (d, 1H), 7.92 (d, 2H), 7.92 (d, , 6.65 (d, 2H), 6.55 (dd, 1H), 6.48 781 48 1H), 7.72-7.38 (m, 5H), 7.82 (d, 2H) 2H), 1.82 (s, 12H), 7.18 (d, IH) 780 49 (M, 3H), 7.82-7.81 (m, 3H), 7.72-7.38 (m, 3H) 2H), 1.82 (s, 12H), 6.85 (d, 2H) 729 50 (M, 2H), 7.72-7.51 (m, 16H), 7.51-7.48 (m, 3H), 7.38 ), 6.85 (s, 2H), 6.79 (d, 2H), 6.68 755 51 2H), 7.38 (d, IH), 7.18 (d, 2H), 7.72 (d, , 6.85 (s, 3H), 6.68 (d, 2H), 1.82 (s, 12H) 780 52 1H), 7.16 (s, 1H), 7.72 (d, 2H), 7.65 (d, 2H), 6.85 (s, 2H), 6.85 (s, 2H) 782 53 2H), 7.29-7.26 (m, 4H), 6.85 (d, 2H), 7.72 (d, (s, 2H), 6.79 (s, 2H), 6.68 (d, 2H), 1.82 828 54 2H), 7.65 (d, IH), 7.85 (d, IH), 7.87 (d, 2H), 6.68 (d, 2H), 2.31-2.06 (m, 4H), 1.82 (s, 6H), 1.66-1.56 731 55 2H), 7.65 (d, 2H), 7.65 (s, 1H), 7.97 (d, , 6.79 (s, 2H), 6.68 (d, 2H), 1.82 (s, 6H) 830 56 2H), 7.82 (s, 2H), 7.72 (d, 2H), 7.62-7.51 (m, m, 4H), 1.82 (s, 12H) 782 57 (M, 3H), 7.64-7.42 (m, 3H), 7.26-7.18 (m, 3H), 6.97 (d, IH), 6.83 (d, IH), 6.82 (s, 679 58 2H), 7.13 (t, IH), 7.63 (d, IH), 7.75 (m, 1H), 6.82 (s, 1H), 6.68 (d, 2H), 6.43 (d, 842 59 (M, 2H), 7.21-7.13 (m, 5H), 7.72-7.72 (m, 3H) 1H), 6.82 (s, 1H), 6.68 (d, 2H), 6.43 (d, 844 60 2H), 7.82 (s, 1H), 7.76-7.72 (m, 3H), 7.65-7.38 (m, 16H), 7.13 4H), 1.82 (s, 6H), 1.66-1.56 (m, 4H), 6.85 (d, 745 61 2H), 7.82 (s, 1H), 7.76-7.72 (m, 3H), 7.65-7.61 (m, 9H), 7.53-7.38 2H), 6.83 (d, 1H), 1.82 (s, 12H), 7.13 (t, 719 62 2H), 7.82 (s, 1H), 7.76-7.72 (m, 4H), 7.65-7.61 (m, 9H), 7.53-7.38 2H), 6.68 (d, 2H), 6.43 (d, 1H), 1.82 719 63 2H), 6.68 (d, 2H), 6.43 (d, 2H), 7.82 (s, 1H), 2.31-2.06 (m, 4H), 1.82 (s, 6H), 1.66-1.56 (m, 4H) 745 64 2H), 6.68 (d, 2H), 7.82 (s, 1H), 7.99 (s, 2H), 6.43 (d, 1 H), 1.82 (s, 6 H) 844 65 2H), 6.85 (s, 1H), 6.79 (d, 1H), 7.79 (d, 2H), 6.68 (d, IH), 6.43 (d, IH), 1.82 679 66 (S, 2H), 6.68 (d, 2H), 6.43 (m, 2H), 7.75-7.82 d, 1 H), 1.82 (s, 6 H) 842 67 (D, 2H), 6.85 (s, 1H), 7.82 (s, 1H) 2H), 6.68 (d, IH), 6.43 (d, IH), 1.82 755 68 2H), 7.05 (s, 1H), 7.82 (s, 1H), 7.98 (s, 1H), 6.85 (s, 1H), 6.71-6.68 (m, 2H), 6.43 755 69 (M, 3H), 7.62-7.42 (m, 23H), 7.16 (d, IH), 6.95 (d, IH) 2H), 6.85 (s, IH), 6.68 (d, IH), 6.43 755 70 (M, 4H), 7.62-7.42 (m, 19H), 7.05 (s, 1H) 1H), 6.82 (s, 1H), 6.85 (d, IH) 755 71 2H), 7.35 (d, 4H), 6.85 (s, 1H), 7.82 (s, 1H), 6.83 (d, 2H), 6.68 (d, 755 72 (S, 1H), 6.68 (d, 1H), 6.43 (d, 2H), 7.82 2H), 1.82 (s, 6H) 693 73 1H), 6.85 (s, 1H), 6.68 (d, 2H), 7.82 (m, 1H), 6.49-6.43 (m, 2H), 1.82 (s, 6H) 693 74 1H), 6.68 (d, 1H), 6.49-6.43 (m, 6H), 7.62 (s, m, 2 H), 1.82 (s, 6 H) 693 75 (D, 2H), 8.12 (s, 1H), 7.99 (d, 1H), 7.82-7. 72 (m, 7H), 7.62-7.42 1H), 6.49-6.43 (m, 2H), 1.82 (s, 6H) 743 76 1H), 7.98 (d, 1H), 7.62 (d, 1H), 7.62 (d, 1H), 6.85 (s, 1H), 6.79 (d, 2H), 6.68 695 77 1H), 7.72 (d, 2H), 7.65-7.48 (m, 2H), 7.97 (d, 2H), 6.82 (d, 2H), 1.82 (s, 12H), 7.28 (s, 735 78 1H), 7.72 (d, 1H), 7.62-7.51 (m, 16H), 7.26-7.16 (d, (d, 1H), 6.82 (d, 1H), 1.82 (s, 6H) 695 79 1H), 7.72 (d, 1H), 7.62 (d, 1H), 7.62 (d, 2H), 6.68 (d, IH), 1.82 (s, 6H), 6.85 (d, IH) 771 80 (M, 2H), 7.97 (d, 1H), 7.91 (d, 1H), 7.82 2H), 6.82 (d, 2H), 1.82 (s, 12H), 7.18 (d, 735 81 (M, 2H), 7.87 (s, 1H), 7.82 (s, 1H) 1H), 6.85 (s, 1H), 6.79 (d, 4H), 6.68 781 82 (M, 2H), 7.87 (s, 1H), 7.82 (s, 1H) 1H), 7.28 (d, 1H), 7.18 (d, 2H), 6.97 (t, ) 781 83 2H), 7.65-7.61 (m, 14H), 7.54-7.48 (m, 3H) 1H), 6.82 (d, 2H), 1.82 (s, 18H), 7.38 (t, 821 84 (M, 3H), 7.87 (s, 1H), 7.82 (s, 1H), 7.73 (d, 2H), 7.65-7.48 (D, 1H), 7.35 (d, 4H), 6.85 (s, 857 85 1H), 7.73 (d, 3H), 7.65-7.61 (m, 12H), 7.51-7.48 (m, 2H), 6.82 (s, 2H), 6.82 (d, 2H) 821 86 (M, 12H), 7.51 (s, 1H), 8.02 (s, 1H), 8.03-7.97 2H), 6.68 (d, 1H), 6.43 (d, 1H), 1.82 (s, 12H) 795 87 (M, 2H), 7.87 (s, 1H), 7.76-7.72 (m, 4H) 2H), 6.68 (d, 1H), 6.49 (d, 1H), 1.82 (s, 12H) 795 88 (M, 3H), 7.87 (s, 1H), 7.82-7.72 (s, 1H) 2H), 6.68 (d, 1H), 6.49 (d, 1H), 1.82 (s, 12H) 795 89 (M, 8H), 7.65-7.38 (m, 18H), 7.18 (d, 1H), 8.08 (d, 1H), 6.85-6.79 (m, 3H), 7.42 (d, 1H), 1.82 805 90 (M, 2H), 7.87 (s, 1H), 7.82 (s, 1H), 7.72-7.48 (d, IH), 6.85 (s, IH), 6.79 (d, 755 91 (D, 2H), 6.43 (d, 2H), 7.63 (s, 1H) d, 2 H), 1.82 (s, 6 H) 769 92 2H), 6.49 (d, 2H), 7.79 (d, IH), 8.12 (s, d, 1 H), 6.43 (d, 1 H), 1.82 (s, 6 H) 769 93 1H), 7.17 (d, 1H), 6.79 (m, 2H), 7.87 (d, 2H), 6.49 (d, 1H), 6.43 (d, 769 94 (M, 2H), 7.79 (s, 1H), 7.82 (s, 1H) d, 4H), 6.43 (d, IH), 1.82 (s, 6H) 755 95 (S, 1H), 7.63 (s, 1H), 7.83-7.79 (m, 2H), 7.67 2H), 6.77 (d, IH), 6.98 (d, IH) 755 96 (M, 3H), 7.18 (t, 1H), 7.92 (d, 1H) 2H), 6.53-6.48 (m, 4H), 1.62 (s, 12H), 6.91 (d, 629 97 (M, 4H), 7.18 (t, 1H), 7.92 (d, 1H) 1H), 7.06 (t, IH), 6.98-6.93 (m, 3H), 6.81-6.77 (m, 2H), 6.65 (s, 12 H) 705 98 1H), 7.92 (d, IH), 7.92 (d, IH), 7.92 (s, , 6.81 (m, 3H), 6.65 (s, 1H), 6.49-6.48 705 99 1H), 7.92 (d, IH), 7.92 (d, IH), 7.92 (s, , 6.81 (d, IH), 6.65 (s, IH), 6.59-6.58 (m, 2H), 6.49-6.48 705 100 (M, 4H), 7.18 (t, 2H), 7.92 (d, 2H) 2H), 6.93 (s, 2H), 6.93 (d, IH) 745 101 (M, 4H), 7.18 (t, 2H), 7.92 (d, 2H) 2H), 6.93 (s, 2H), 6.93 (d, IH) 745 102 (M, 12H), 7.01-6.93 (m, 2H), 7.92 (s, 1H) 2H), 6.48-6.42 (m, 3H), 1.62 (s, 12H) 870 103 (M, 5H), 6.93 (s, 1H), 7.92 (d, 1H) 1H), 6.81 (d, 1H), 6.65 (s, 1H), 6.59 (d, 2H), 6.48 782 104 1H), 7.52-7.41 (m, 15H), 7.31-7.28 (m, 3H), 7.77 (d, (m, 3H), 7.18 (t, IH), 6.93 (t, IH), 6.81 (d, IH), 6.65 , 12H) 755 105 2H), 7.62 (s, 1H), 7.56-7.52 (m, 3H), 7.45-7.41 (m, 9H), 7.33-7.18 2H), 6.23 (d, 1H), 1.62 (s, 12H), 6.93 (d, 719 106 (M, 2H), 7.41-7.41 (m, 9H), 7.31-7.15 (m, 7H) 2H), 6.29 (d, 1H), 6.62 (s, 1H), 6.97 (d, 719 107 (M, 2H), 6.93 (s, 1H), 7.81 (d, 1H) 2H), 6.48 (d, IH), 6.23 (d, IH), 1.62 (s, 6H) 679 108 (M, 4H), 7.18 (t, 2H), 7.92 (d, 2H) (D, 2H), 6.93 (d, 2H), 6.81 (d, 2H) 745 109 2H), 7.45-7.18 (m, 24H), 6.65 (s, 1H), 6.59 (d, 4H) , 6.48 (d, 1 H), 1.62 (s, 12 H) 782 110 2H), 7.45-7.18 (m, 2H), 7.06 (t, 1H), 6.98 (d, 2H) , 6.77 (t, IH), 6.65 (s, IH) 782 111 (S, 1H), 7.65 (d, 1H), 7.92 (s, 1H) , 6.48 (t, 1 H), 1.62 (s, 12 H) 858 112 (M, 8H), 7.41-7.41 (m, 14H), 7.31-7.18 (m, 8H) 6.65 (s, 1H), 6.59 (d, 4H), 6.48 (t, 872 113 2H), 6.59 (d, 4H), 6.23 (m, 2H), 7.92 (s, d, 1 H), 1.62 (s, 6 H) 846 114 1H), 7.79 (d, 1H), 7.79 (d, 1H), 7.75 (m, 2H), 7.65 (s, 6 H) 665

Comparative Example  compound

< alpha -NPD > < EMI ID =

<Formula e> <Formula 114>

Comparative Example  One

(4,4 ', 4 &quot; -tris (N-naphthalen-2-yl) phthalocyanine), using compound f represented by the following formula f as a fluorescent blue host and using compound g represented by the following formula g as a fluorescent blue dopant: 2-yl) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene- (30 nm) / compound f + compound g (30 nm) / Alq ₃ (25 nm) was used as an organic light emitting device having the following structure: ITO / 2-TNATA / Liq (1 nM) / Al (100 nM).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a 60 nm thick hole injection layer. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by Formula f and a compound represented by Formula g (doping ratio: 4 wt%) were vacuum-deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 25 nm to form an electron transporting layer. Liq 1 nm (electron injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to produce an organic light emitting device as shown in Table 3. This is referred to as Comparative Sample 1.

    <Formula f> <Formula g>

Comparative Example  2 to 4

An organic light emitting device was prepared in the same manner as in Comparative Example 1 except that the above-mentioned compounds d, e, and 114 were used as a hole transport layer instead of? -NPD used as a hole transport layer. These are referred to as Comparative Examples 2 to 4, respectively.

Comparative Example  5

In Comparative Example 1, using a compound d represented by the formula (d) as an electron-blocking compound between the hole transport layer α-NPD and the light emitting layer (formula f + g - doping rate: 4%), A light emitting device was prepared: ITO / 2-TNATA (60 nm) /? -NPD (30 nm) / compound d (10 nm) / compound f + compound g (30 nm) / Alq ₃ nm) / Al (100 nm).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a 60 nm thick hole injection layer. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound d was deposited on the hole transport layer to a thickness of 10 nm to form an electron blocking layer. A compound f represented by the formula f and a compound g represented by the formula g (g doping ratio: 4 wt%) were vacuum deposited to form a light emitting layer with a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 25 nm to form an electron transporting layer. Liq 1 nm (electron injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to produce an organic light emitting device as shown in Table 3. This is referred to as Comparative Example 5.

Example  1 to 8

Except that the compounds 6, 7, 13, 31, 62, 78, 81, and 88 shown in Table 1 were used as a hole transport layer through sublimation purification, respectively, instead of? -NPD used as a hole transport layer. An organic light emitting device was fabricated in the same manner as in Table 3. These are referred to as Examples 1 to 8, respectively.

Example  9-11

In the same manner as in Comparative Example 4, except that Compound 98, 108, and 112 shown in Table 1 were used as an electron blocking layer through a sublimation purification process in place of Compound d used as an electron blocking layer in Comparative Example 4, A light emitting device was prepared and shown in Table 3. These are referred to as Examples 9 to 11, respectively.

Evaluation example  One: Comparative Example  1 to 5 and Example  Evaluation of luminescence characteristics and life span of 1 to 11

Light emission luminance and luminous efficiency were evaluated using Keithley source meter "2400" and KONIKA MINOLTA "CS-2000" for Comparative Examples 1 to 5 and Examples 1 to 11.

The time (LT97) at which the luminance (L) reached 97% on the basis of the initial luminance (L ₀ ) of 1000 nits was measured using a M6000S lifetime measuring device of Mac Science Inc., and the results are shown in Table 3 below.

Sample No. Hole transportation
compound
No. Electronic blocking
compound
No. Voltage
OP. V Luminance
[cd / m ² ] efficiency
[cd / A] life span
[LT97] Comparative Example 1 alpha -NPD - 4.6 515 5.2 16.0 Comparative Example 2 d - 4.5 526 5.3 25.4 Comparative Example 3 e - 4.5 525 5.3 22.1 Comparative Example 4 114 - 4.8 512 5.1 14.2 Example 1 6 - 4.2 551 5.5 68.7 Example 2 7 - 4.2 571 5.7 42.2 Example 3 13 - 3.9 555 5.6 56.7 Example 4 31 - 3.9 550 5.5 55.8 Example 5 62 - 4.1 549 5.5 59.9 Example 6 78 - 4.2 541 5.4 62.4 Example 7 81 - 4.1 568 5.7 70.2 Example 8 88 - 4.0 555 5.6 61.7 Comparative Example 5 alpha -NPD d 4.3 594 5.9 80.3 Example 9 alpha -NPD 98 4.3 601 6.0 108.2 Example 10 alpha -NPD 108 4.2 621 6.2 82.2 Example 11 alpha -NPD 112 4.2 611 6.1 96.7

As shown in Table 3, Examples 1 to 11 exhibited low voltage driving and improved luminescent characteristics as compared with Comparative Examples 1 to 5.

As shown in Table 3, Examples 1 to 11 exhibited improved life characteristics compared to Comparative Examples 1 to 5. Particularly, these compounds of fluorene, dibenzofurane or dibenzothiophenamine derivatives exhibit excellent performance and life span, with aryl groups substituted at the 1 and 3 positions of fluorene.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (10)

Gt; 1-7, 9-14, 19-21, 23-29, 31-50, 52-56, 58-66, 69-77, 79-81, 83-94, 96, 98-109 and 111-113 Wherein the organic compound is a diarylfluorene amine derivative organic compound.

delete delete delete delete delete The method according to claim 1,
The diarylfluorene amine derivative organic compound is used as a material for a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, or an electron injecting layer in a material for an organic EL device
Diarylfluorene amine derivatives Organic compounds.
At least one organic thin film layer sandwiched between a cathode and an anode, wherein the organic thin film layer has a multi-layer structure including at least one light emitting layer, and at least one organic thin film layer in the organic thin film layer other than the light emitting layer or the light emitting layer Wherein the layer comprises the diarylfluorene amine derivative organic compound according to claim 1 alone or a mixture of two or more thereof.
9. The method of claim 8,
The organic thin film layer includes a hole transporting region interposed between the anode and the light emitting layer and including at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer,
Organic electroluminescent device.
10. The method of claim 9,
Wherein the hole transport region further comprises a p-dopant
Organic electroluminescent device.

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